外加磁场下微介孔型b、c复合轴向ZSM-5分子筛的合成及其在甲醇制芳烃中的应用
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摘要
采用水热合成法辅加磁场成功制备了b、c复合轴向型ZSM-5分子筛,考察了磁感线分布、磁场强度和作用时间对ZSM-5分子筛结构和甲醇芳构化反应催化性能的影响。结果表明,磁场强度和作用时间可以精密调控材料的孔径分布;磁场强度47.1 m T,平行磁感线位置下作用5 h,合成材料具有b、c-复合轴取向结构,介孔的比表面积和孔容比分别达到67%和78%。相比常规ZSM-5,新材料具有更高的催化稳定性,反应20 h后的甲醇转化率和芳烃收率保持在98%和36%以上。
The micro-mesoporous b,c-composite axis oriented ZSM-5 zeolite is successfully obtained by hydrothermal synthesis method with external magnetic field. The effects of magnetic induction line distribution,magnetic field strength and treatment time on the structure of prepared ZSM-5 zeolite and its catalytic performance in methanol to aromatics( MTA) are investigated.It is showed that the pore size distribution of the material can be precisely regulated by the magnetic field strength and treatment time.When the magnetic field strength is 47. 1 m T and treatment time is 5 h under parallel magnetic induction line,the prepared ZSM-5 zeolite will have b,c-composite axis oriented structure,and the total specific surface area and pore volume ratio of its mesopore reaches 67% and 78% respectively. Compared with the conventional ZSM-5,the new one prepared has more excellent catalytic stability. In MTA over the prepared micromesoporous b,c-composite axis oriented ZSM-5 zeolite,the conversion of methanol and the yield of aromatics can still maintain above 98% and 36% respectively after 20 h of reaction.
The micro-mesoporous b,c-composite axis oriented ZSM-5 zeolite is successfully obtained by hydrothermal synthesis method with external magnetic field. The effects of magnetic induction line distribution,magnetic field strength and treatment time on the structure of prepared ZSM-5 zeolite and its catalytic performance in methanol to aromatics( MTA) are investigated.It is showed that the pore size distribution of the material can be precisely regulated by the magnetic field strength and treatment time.When the magnetic field strength is 47. 1 m T and treatment time is 5 h under parallel magnetic induction line,the prepared ZSM-5 zeolite will have b,c-composite axis oriented structure,and the total specific surface area and pore volume ratio of its mesopore reaches 67% and 78% respectively. Compared with the conventional ZSM-5,the new one prepared has more excellent catalytic stability. In MTA over the prepared micromesoporous b,c-composite axis oriented ZSM-5 zeolite,the conversion of methanol and the yield of aromatics can still maintain above 98% and 36% respectively after 20 h of reaction.
引文
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[2]Ali K A,Abdullah A Z,Mohamed A R.Recent development in catalytic technologies for methanol synthesis from renewable sources:A critical review[J].Renewable&Sustainable Energy Reviews,2015,44(32):508-518.
[3]顾祥万.对二甲苯市场分析及开发建议[J].化工进展,2014,33(6):1628-1631.
[4]Conte M,Lopezsanchez J A,He Q,et al.Modified zeolite ZSM-5 for the methanol to aromatics reaction[J].Catalysis Science&Technology,2011,2(2):105-112.
[5]Niu X,Gao J,Wang K,et al.Influence of crystal size on the catalytic performance of H-ZSM-5 and Zn/H-ZSM-5 in the conversion of methanol to aromatics[J].Research Gate,2017,157:99-107.
[6]Khodakov A Y,Chu W,Fongarland P.Advances in the development of novel cobalt Fischer-Tropsch catalysts for synthesis of long-chain hydrocarbons and clean fuels[J].Chemical Reviews,2007,107(5):1692-1744.
[7]Li S,Demmelmaier C,Itkis M,et al.Micropatterned oriented zeolite monolayer films by direct in situ crystallization[J].Chemistry of Materials,2003,15(14):2687-2689.
[8]马通,耿祖豹,李冰,等.不同模板制备ZSM-5分子筛的酸性特征及催化裂解性能差异[J].化工学报,2016,67(8):3374-3379.
[9]张娜,徐亚荣,徐新良,等.Zn/ZSM-5催化剂在甲醇制芳烃(MTA)反应中的失活与再生[J].天然气化工(C1化学与化工),2015,40(6):18-21.
[10]董光斌.Zn引入量对ZSM-5甲醇芳构化反应性能的影响[J].石油化工应用,2015,34(7):118-120.
[11]郭春垒,方向晨,贾立明,等.分子筛催化剂积炭失活行为探讨[J].工业催化,2011,19(124):15-20.
[12]Chu R Z,Hou W X,Xu T T,et al.Effect of modification on Pd dispersion,acidity,sulfur resistance and catalysis of Pd/Al-MCM-41zeolite[J].Journal of Porous Materials,2017,24(2):1-8.